CN106366998B - Liquid crystal sealing agent and liquid crystal display cell using the same - Google Patents

Liquid crystal sealing agent and liquid crystal display cell using the same Download PDF

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CN106366998B
CN106366998B CN201610491657.1A CN201610491657A CN106366998B CN 106366998 B CN106366998 B CN 106366998B CN 201610491657 A CN201610491657 A CN 201610491657A CN 106366998 B CN106366998 B CN 106366998B
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liquid crystal
sealing agent
dropping method
crystal sealing
component
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CN106366998A (en
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内藤正弘
太田英之
坂野常俊
竹居祥行
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1341—Filling or closing of cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention relates to a liquid crystal sealing agent and a liquid crystal display cell using the same. The present invention relates to a liquid crystal sealing agent for a liquid crystal dropping method which is cured by heat, and provides a liquid crystal sealing agent for a liquid crystal dropping method which has extremely low wiring corrosion resistance after a moisture resistance test and is excellent in general characteristics such as low liquid crystal contamination and adhesive strength, and thus realizes high definition, high-speed response, low-voltage driving, and long life of a liquid crystal display element. A liquid crystal sealing agent for liquid crystal dropping method, which comprises (A) a curable compound, wherein the water absorption rate of the cured product obtained by heat curing at 130 ℃ for 1 hour without ultraviolet irradiation is 2.0% or less as measured according to JIS-K7209, and the moisture permeability of the cured product is 130g/m as measured according to JIS-K7129224h or less.

Description

Liquid crystal sealing agent and liquid crystal display cell using the same
Technical Field
The present invention relates to a liquid crystal sealing agent for a liquid crystal dropping method, which is cured by heat. More specifically, the present invention relates to a liquid crystal sealing agent for use in a liquid crystal dropping method, which has extremely low wiring corrosion after a humidity resistance test and is excellent in general characteristics such as low liquid crystal contamination and adhesive strength.
Background
With the recent increase in size of liquid crystal display units, so-called liquid crystal dropping methods, which are more mass-producible, have been proposed as methods for manufacturing liquid crystal display units (see patent documents 1 and 2). Specifically, the method for manufacturing a liquid crystal display unit includes: liquid crystal is sealed by dropping liquid crystal on the inside of a bank of liquid crystal sealant formed on one substrate and then attaching the other substrate.
However, the liquid crystal dropping method has the following problems: since the liquid crystal sealant in an uncured state is in contact with the liquid crystal, the components of the liquid crystal sealant are dissolved (eluted) into the liquid crystal at this time, and the resistance value of the liquid crystal is lowered, thereby causing a display failure in the vicinity of the seal.
In order to solve this problem, a photothermal liquid crystal sealing agent is currently used as a liquid crystal sealing agent for a liquid crystal dropping method, and has been put into practical use (patent documents 3 and 4). The liquid crystal dropping method using the liquid crystal sealing agent is characterized in that the liquid crystal sealing agent sandwiched between the substrates is irradiated with light to be cured once, and then is cured twice by heating. According to this method, the uncured liquid crystal sealing agent can be rapidly cured by light, and dissolution (elution) of the liquid crystal sealing agent component into the liquid crystal can be suppressed. Further, in the case of only photocuring, there is a problem that adhesive strength is insufficient due to curing shrinkage or the like at the time of photocuring, but if the photo-thermal combination type is used, there are the following advantages: the stress relaxation effect can be obtained by the secondary curing by heating, and the above problem can also be solved.
The photo-thermal curing type liquid crystal sealing agent used for the liquid crystal dropping method has been put into practical use, and thus the liquid crystal dropping method has become a commonly used method.
The practical use of the liquid crystal dropping method enables easy manufacture of a large-sized liquid crystal display unit, which results in the spread of liquid crystal displays.
On the other hand, this liquid crystal dropping method sometimes has a disadvantage in terms of the quality of the liquid crystal display unit produced. One of them is a problem that a defect occurs in driving of the liquid crystal after the humidity resistance reliability. This problem is a problem that occurs even in a liquid crystal display unit manufactured by a conventional liquid crystal injection method, but is particularly significant in a liquid crystal display unit manufactured by a liquid crystal dropping method. Various attempts have been made to solve this problem. For example, the reaction rate is increased by adding a thermal radical polymerization initiator and a curing accelerator; a material having low solubility in liquid crystal is used as a constituent component.
However, even through these studies, a liquid crystal sealant for a liquid crystal dropping method which sufficiently solves the above problems has not been achieved.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 63-179323
Patent document 2: japanese laid-open patent publication No. 10-239694
Patent document 3: japanese patent No. 3583326
Patent document 4: japanese patent laid-open publication No. 2004-61925
Patent document 5: japanese patent laid-open publication No. 2004-126211
Patent document 6: japanese laid-open patent publication No. 2009-8754
Patent document 7: international publication No. 2008/004455
Disclosure of Invention
Problems to be solved by the invention
The present invention relates to a liquid crystal sealing agent for a liquid crystal dropping method which is cured by heat, and provides a liquid crystal sealing agent for a liquid crystal dropping method which has extremely low wiring corrosion resistance after a moisture resistance test and is excellent in general characteristics such as low liquid crystal contamination and adhesive strength, and thus realizes high definition, high-speed response, low-voltage driving, and long life of a liquid crystal display element.
Means for solving the problems
The present inventors have conducted intensive studies in order to solve the above-mentioned problem of the driving defect, and as a result, have found that the problem is caused by corrosion of wiring after a moisture resistance test, which is affected by moisture permeability and water absorption of a portion after curing is performed almost only by heat and curing is insufficient by ultraviolet rays such as under a black matrix, and have completed the invention of the present application.
That is, the present invention relates to the following 1) to 14). In the present specification, the term "(meth) acrylic acid" means "acrylic acid" and/or "methacrylic acid". In addition, the "liquid crystal sealant used in the liquid crystal dropping method" may be abbreviated as "liquid crystal sealant".
1)
A liquid crystal sealing agent for a liquid crystal dropping method, which contains (A) a curable compound,
the cured product obtained by heat curing at 130 ℃ for 1 hour without ultraviolet irradiation has a water absorption of 2.0% or less as measured according to JIS-K7209 and a moisture permeability of 130g/m as measured according to JIS-K7129224h or less.
2)
The liquid crystal sealing agent for liquid crystal dropping method as described in the above 1), which further contains (B) a thermal radical polymerization initiator.
3)
The liquid crystal sealing agent for liquid crystal dropping method according to 1) or 2), wherein the thermal radical polymerization initiator of the component (B) is a thermal radical polymerization initiator which does not contain an oxygen-oxygen bond (-O-) and a nitrogen-nitrogen bond (-N ═ N-) in a molecule.
4)
The liquid crystal sealant for liquid crystal dropping method as described in any one of 1) to 3) above, which further contains (C) a photo radical polymerization initiator.
5)
The liquid crystal sealing agent for liquid crystal dropping method as described in any of 1) to 4) above, further comprising (D) a filler, wherein the content of the filler in the total amount of the liquid crystal sealing agent is 20% by mass or more.
6)
The liquid crystal sealant for liquid crystal dropping method as described in any of the above 1) to 5), wherein the above component (D) is a mixture of (D-1) an organic filler and (D-2) an inorganic filler.
7)
The liquid crystal sealing agent for a liquid crystal dropping method as described in any of the above 1) to 6), wherein the content of the inorganic filler of the component (D-2) in the total amount of the liquid crystal sealing agent is 20% by mass or more.
8)
The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above 1) to 7), wherein the curable compound of the component (a) is an epoxy (meth) acrylate compound.
9)
The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above 1) to 7), wherein the curable compound of the above component (a) is a mixture of an epoxy (meth) acrylate compound and an epoxy compound.
10)
The liquid crystal sealant for liquid crystal dropping method as described in any one of 1) to 9) above, which further contains (E) a heat curing agent.
11)
The liquid crystal sealing agent for liquid crystal dropping method according to the above 10), wherein the component (E) heat-curing agent is an organic hydrazide.
12)
The liquid crystal sealant for liquid crystal dropping method as described in any one of 1) to 11) above, which further contains (F) a silane coupling agent.
13)
A method for manufacturing a liquid crystal display unit, characterized in that a liquid crystal is dropped on the inside of the bank of the liquid crystal sealing agent for the liquid crystal dropping method described in any one of 1) to 12) above formed on one substrate in a liquid crystal display unit including two substrates, and then the other substrate is attached, and then curing is performed by light and/or heat.
14)
A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent for liquid crystal dropping method described in any one of 1) to 12) above.
Effects of the invention
The liquid crystal sealing agent for the liquid crystal dropping method of the present invention is extremely useful as a liquid crystal sealing agent for a liquid crystal display element because it can suppress wiring corrosion to the maximum extent, and is also excellent in low liquid crystal contamination property and adhesive strength.
Drawings
Fig. 1 is a view showing a curing width of a light shielding portion. After the chromium coating is etchedThe center of the engraved glass substrate was coated with a liquid crystal sealant containing 1 wt% of 5 μm glass fiber, and the glass substrate was bonded to a counter substrate using a black matrix substrate and fixed with a clip (before ultraviolet irradiation). The chromium-etched glass substrate was irradiated with 3000mJ/cm light from the side of the substrate2The bonded two substrates were peeled off, and the portion shielded from light below the chrome was confirmed by a microscope, and the curing width of the light shielding portion was measured.
Detailed Description
The liquid crystal sealing agent of the present invention contains (a) a curable compound.
The component (a) is not particularly limited as long as it is a compound which undergoes polymerization reaction by light or heat, and examples thereof include: a curable compound having a (meth) acryloyl group, a curable compound having an epoxy group, and the like.
Examples of the curable compound having a (meth) acryloyl group include: (meth) acrylates, epoxy (meth) acrylates, and the like. As the (meth) acrylic acid ester, there may be mentioned: benzyl methacrylate, cyclohexyl methacrylate, glycerol dimethacrylate, glycerol triacrylate, EO-modified glycerol triacrylate, pentaerythritol acrylate, trimethylolpropane triacrylate, tris (acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, phloroglucinol triacrylate, and the like. The epoxy (meth) acrylate can be obtained by a known method by reacting an epoxy compound with (meth) acrylic acid. The epoxy compound to be used as a raw material is not particularly limited, and preferably a bifunctional or higher epoxy compound, and examples thereof include: bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol a novolac type epoxy compounds, bisphenol F novolac type epoxy compounds, alicyclic epoxy compounds, aliphatic chain epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, hydantoin type epoxy compounds, isocyanurate type epoxy compounds, phenol novolac type epoxy compounds having a trishydroxyphenylmethane skeleton, and diglycidyl etherate of bifunctional phenols such as catechol and resorcinol, diglycidyl etherate of bifunctional alcohols, halides and hydrides thereof, and the like. Among them, from the viewpoint of liquid crystal contamination, epoxy compounds having a resorcinol skeleton, for example, resorcinol diglycidyl ether and the like are preferable. The ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process adaptability and liquid crystal contamination.
Therefore, the curable compound having a (meth) acryloyl group is preferably a curable compound having a (meth) acryloyl group and further having a resorcinol skeleton, and examples thereof include acrylate of resorcinol diglycidyl ether and methacrylate of resorcinol diglycidyl ether.
Examples of the curable compound having an epoxy group include epoxy compounds. The epoxy compound is not particularly limited, and preferably a bifunctional or higher epoxy compound, and examples thereof include: bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol a novolac type epoxy compounds, bisphenol F novolac type epoxy compounds, alicyclic epoxy compounds, aliphatic chain epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, hydantoin type epoxy compounds, isocyanurate type epoxy compounds, phenol novolac type epoxy compounds having a trishydroxyphenylmethane skeleton, and diglycidyl etherate of bifunctional phenols, diglycidyl etherate of bifunctional alcohols, halides and hydrides thereof. Among them, from the viewpoint of liquid crystal contamination, bisphenol type epoxy compounds and novolak type epoxy compounds are more preferable.
Two or more of the curable compound having a (meth) acryloyl group and the curable compound having an epoxy group may be used in combination, and it is one of particularly preferred embodiments of the present invention to use a (meth) acrylated epoxy compound in combination with an epoxy compound.
The content of the component (A) in the liquid crystal sealing agent of the present invention is usually 30 to 75% by mass, preferably 40 to 65% by mass, and particularly when an epoxy compound is used in combination with a (meth) acrylated epoxy compound, the content of the epoxy compound in the component (A) is usually 3 to 30% by mass, preferably 5 to 20% by mass, more preferably 8 to 15% by mass.
The liquid crystal sealing agent of the present invention has a water absorption of 2.0% or less (wherein the test conditions are 60 ℃ and 90% environment) measured according to JIS-K7209(D method) of a cured product obtained by heat curing at 130 ℃ for 1 hour without ultraviolet irradiation. This is because: the absorbed moisture in the liquid crystal sealant promotes decomposition of organic matter in the liquid crystal sealant and carries out the decomposition products, impurity ions, to the outside of the liquid crystal sealant.
The water absorption is preferably 1.8% or less, more preferably 1.6% or less.
The liquid crystal sealing agent of the present invention has a moisture permeability of 130g/m as measured by a method in accordance with JIS-K7129 (method A) of a cured product obtained by heat curing at 130 ℃ for 1 hour without ultraviolet irradiation224h or less. This is because: moisture permeating through the liquid crystal sealing agent has a large influence on the corrosion of the wiring. When LyssyL80-5000 manufactured by Systech illinois is used, the measurement according to JIS-K7129 (method A) can be performed. The test was carried out at a set test temperature of 60 ℃.
The moisture permeability is preferably 110g/m224h or less, more preferably 90g/m224h or less.
The liquid crystal sealing agent of the present invention can improve the curing speed and the curing degree by using (B) a thermal radical polymerization initiator.
The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, and examples thereof include: organic peroxides, azo compounds, benzoin ether compounds, acetophenone compounds, benzopinacol, and the like, and benzopinacol is preferably used. For example, Kayamek is commercially available as an organic peroxideRTM A、M、R、L、LH、SP-30C、Perkadox CH-50L、BC-FF、Cadox B-40ES、Perkadox 14、TrigonoxRTM 22-70E、23-C70、121、121-50E、121-LS50E、21-LS50E、42、42LS、KayaesterRTM P-70、TMPO-70、CND-C70、OO-50E、AN、KayabutylRTM B、Perkadox 16、KayacarbonRTMBIC-75, AIC-75 (chemical AKZO Co., Ltd.), PermekRTM N、H、S、F、D、G、PerhexaRTMH、HC、Per TMH、C、V、22、MC、PercureRTM AH、AL、HB、PerbutylRTM H、C、ND、L、PercumylRTM H、D、PeroylRTM IB、IPP、PeroctaRTMND (manufactured by Nichisu oil Co., Ltd.) and the like.
Further, VA-044, V-070, VPE-0201, VSP-1001 (manufactured by Wako pure chemical industries, Ltd.) and the like are commercially available as azo compounds. In this specification, the superscript RTM is a registered trademark.
The component (B) is preferably a thermal radical polymerization initiator having no oxygen-oxygen bond (-O-) or nitrogen-nitrogen bond (-N ═ N-) in the molecule. This is because: a thermal radical polymerization initiator having an oxygen-oxygen bond (-O-) or a nitrogen-nitrogen bond (-N ═ N-) in the molecule generates a large amount of oxygen and nitrogen when generating radicals, and therefore, may be cured in a state where air bubbles remain in the liquid crystal sealing agent, and may deteriorate the properties such as adhesive strength. Particularly preferred are thermal radical polymerization initiators of the benzopinacol type (including ones obtained by chemically modifying benzopinacol). Specifically, there may be mentioned: benzopinacol, 1, 2-dimethoxy-1, 1,2, 2-tetraphenylethane, 1, 2-diethoxy-1, 1,2, 2-tetraphenylethane, 1, 2-diphenoxy-1, 1,2, 2-tetraphenylethane, 1, 2-dimethoxy-1, 1,2, 2-tetrakis (4-methylphenyl) ethane, 1, 2-diphenoxy-1, 1,2, 2-tetrakis (4-methoxyphenyl) ethane, 1, 2-bis (trimethylsiloxy) -1,1,2, 2-tetraphenylethane, 1, 2-bis (triethylsiloxy) -1,1,2, 2-tetraphenylethane, 1, 2-bis (tert-butyldimethylsiloxy) -1,1,2, 2-tetraphenylethane, 1-hydroxy-2-trimethylsilyloxy-1, 1,2, 2-tetraphenylethane, 1-hydroxy-2-triethylsilyloxy-1, 1,2, 2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsilyloxy-1, 1,2, 2-tetraphenylethane and the like, preferably 1-hydroxy-2-trimethylsilyloxy-1, 1,2, 2-tetraphenylethane, 1-hydroxy-2-triethylsilyloxy-1, 1,2, 2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsilyloxy-1, 1,2, 2-tetraphenylethane, 1, 2-bis (trimethylsilyloxy) -1,1,2, 2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsilyloxy-1, 1,2, 2-tetraphenylethane, 1, 2-bis (trimethylsilyloxy) -1,1,2, 2-tetraphenylethane, particularly preferably 1, 2-bis (trimethylsilyloxy) -1,1,2, 2-tetraphenylethane.
The benzopinacol is commercially available from Tokyo Kasei Kogyo, Wako pure chemical industries, Ltd. In addition, etherification of the hydroxyl group of benzopinacol can be easily performed by a known method. The hydroxyl group of benzopinacol can be silylized by heating the corresponding benzopinacol and various silylating agents in the presence of a basic catalyst such as pyridine. Examples of the silylating agent include generally known Trimethylchlorosilane (TMCS), Hexamethyldisilazane (HMDS), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), Triethylchlorosilane (TECS) as a triethylsilylating agent, and tert-butylmethylsilane (TBMS) as a tert-butyldimethylsilylating agent. These reagents are readily available from silicon derivative manufacturers and the like. The amount of the silylation agent to be reacted is preferably 1.0 to 5.0 times by mol based on 1 mol of the hydroxyl group of the target compound. More preferably 1.5 to 3.0 times by mol. When the amount is less than 1.0 time by mol, the reaction efficiency is poor and the reaction time is long, so that thermal decomposition is promoted. When the molar ratio is more than 5.0 times, the separation becomes poor at the time of recovery or purification becomes difficult.
The component (B) is preferably dispersed uniformly and finely. When the average particle size is too large, it becomes a bad factor such that a gap is not formed well when the upper and lower glass substrates are bonded when a liquid crystal display cell having a narrow gap is manufactured, and therefore, it is preferably 5 μm or less, more preferably 3 μm or less. The thickness of the film may be reduced without limitation, but the lower limit is usually about 0.1. mu.m. The particle diameter can be measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by セイシン, LMS-30).
The content of the component (B) is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass, and particularly preferably 0.001 to 3% by mass, based on the total amount of the liquid crystal sealing agent.
The liquid crystal sealing agent of the present invention can be prepared as a photo-thermal liquid crystal sealing agent using (C) a photo radical polymerization initiator.
The photo radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by irradiation with ultraviolet rays or visible light and initiates a chain polymerization reaction, and examples thereof include: benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methyl propiophenone, 2-methyl- [4- (methylthio) phenyl]2-morpholino-1-propane, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide, etc. Specifically, there may be mentioned: IRGACURERTM 651、184、2959、127、907、369、379EG、819、784、754、500、OXE01、OXE02、DAROCURERTM 1173、LUCIRINRTMTPO (both manufactured by BASF corporation) and SEIKUOLRTMZ, BZ, BEE, BIP, BBI (all of Seiko chemical Co., Ltd.), and the like.
In addition, from the viewpoint of liquid crystal contamination, it is preferable to use a photo radical polymerization initiator having a (meth) acryloyl group in the molecule, for example, a reaction product of 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one. This compound can be produced by the method described in international publication No. 2006/027982.
In addition, from the viewpoint of improving curability of a light-shielding portion which cannot be sufficiently reached by light due to wiring and a black matrix, it is preferable that the extinction coefficient at 350nm measured in acetonitrile is 500ml g-1Cm or more. For example, IRGACURERTM 651、907、369、379EG、819、784、OXE01、OXE02、LUCIRINRTMTPO (all manufactured by BASF Co., Ltd.), diethyl thioxanthone, and,Benzophenone, and the like.
The content of the photo radical polymerization initiator (C) which can be used in the liquid crystal sealing agent of the present invention in the liquid crystal sealing agent is usually 0.1 to 20% by mass, preferably 0.2 to 15% by mass, based on the total amount of the liquid crystal sealing agent of the present invention.
The liquid crystal sealing agent of the present invention can achieve an improvement in adhesive strength by using (D) a filler. The filler may be (D-1) an organic filler, or (D-2) an inorganic filler, or a mixture thereof, but since each of them has a different function, a mixture of both is preferable.
The content of the filler (D) is usually 5 to 70% by mass, preferably 10 to 60% by mass, based on the total amount of the liquid crystal sealing agent. When the content of the filler (D) is 20% by mass or more, the effects of the present invention are particularly remarkably exhibited, and particularly preferably 20 to 50% by mass.
As the organic filler as the component (D-1), there may be mentioned, for example: urethane fine particles, acrylic fine particles, styrene olefin fine particles, and silicone fine particles. The silicone microparticles are preferably KMP-594, KMP-597, KMP-598 (manufactured by shin-Etsu chemical industries), TrefilRTME-5500, 9701, and EP-2001 (manufactured by Torredo Corning Co., Ltd.), JB-800T, HB-800BK (manufactured by Kogyo Co., Ltd.) is preferable as the urethane fine particles, and Rabalon is preferable as the styrene fine particlesRTMT320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C and SJ6300C (manufactured by Mitsubishi chemical Co., Ltd.), and SEPTON is preferable as the styrene olefin fine particlesRTM SEPS2004、SEPS2063。
These organic fillers may be used alone or in combination of two or more. In addition, two or more kinds may be used to form the core-shell structure. Among them, acrylic fine particles and silicone fine particles are preferable.
In the case of using the acrylic fine particles, an acrylic rubber having a core-shell structure containing two types of acrylic rubbers is preferable, and an acrylic rubber having a core layer of n-butyl acrylate and a shell layer of methyl methacrylate is particularly preferable. It is prepared from ZEFIACRTMThe form of F-351 is represented by the Ack industrial strainAnd (4) selling by society.
Further, examples of the silicone fine particles include: organopolysiloxane crosslinked powder, linear dimethylpolysiloxane crosslinked powder, and the like. Further, the composite silicone rubber may be one in which an organic silicon compound (for example, a polyorganosilsesquioxane compound) is coated on the surface of the silicone rubber. Among these fine particles, silicone rubber of a linear dimethylpolysiloxane crosslinked powder or composite silicone rubber fine particles of a linear dimethylpolysiloxane crosslinked powder coated with an organosilicon compound are particularly preferable. These silicone fine particles may be used alone, or two or more of them may be used in combination. Further, the shape of the rubber powder may preferably be a spherical shape with little increase in viscosity after addition. When the component (D) is used in the liquid crystal sealing agent of the present invention, the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the liquid crystal sealing agent.
As the inorganic filler as the component (D-2), there may be mentioned: silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, and the like, and preferably includes fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, and preferably silica, alumina, talc. These inorganic fillers may be used in combination of two or more.
If the average particle size of the inorganic filler is too large, it becomes a bad factor such that a gap is not formed well when the upper and lower glass substrates are bonded to each other when a liquid crystal cell having a narrow gap is manufactured, and therefore, it is appropriate that the average particle size of the inorganic filler is 2000nm or less, preferably 1000nm or less, and more preferably 300nm or less. The lower limit of the average particle diameter of the inorganic filler is preferably about 10nm, more preferably about 100 nm. The particle diameter can be measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by セイシン Co., Ltd.; LMS-30).
When the inorganic filler is used in the liquid crystal sealing agent of the present invention, the effect of the present invention is more remarkable when the content of the inorganic filler is 20 mass% or more and the content of the inorganic filler may be about 10 to about 50 mass% in the total amount of the liquid crystal sealing agent. Particularly preferably 20 to 50 mass%.
The liquid crystal sealing agent of the present invention may contain (E) a thermosetting agent.
The thermal curing agent is a thermal curing agent which does not generate radicals by heating, unlike the thermal radical polymerization initiator of the component (B). Specifically, there may be mentioned those which undergo nucleophilic reaction by an unshared electron pair or an anion in the molecule, for example, polyamines, polyphenols, organic hydrazide compounds, and the like. However, the present invention is not limited thereto. Among them, organic hydrazide compounds are particularly preferably used. Examples thereof include: aromatic hydrazides include terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2, 6-naphthalenedicarboxylic acid dihydrazide, 2, 6-pyridinedihydrazide, 1,2, 4-benzenetrihydrazide, 1,4,5, 8-naphthalenetetracarboxylic acid tetrahydrazide, pyromellitic acid tetrahydrazide, and the like. In addition, if the aliphatic hydrazide compound is used, for example, the following compounds are mentioned: dihydrazide compounds having a hydantoin skeleton, preferably a valine hydantoin skeleton (skeleton in which the carbon atom of the hydantoin ring is replaced with an isopropyl group), tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, 1, 4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N' -hexamethylenebis-semicarbazide, citric acid trihydrazide, nitrilotriacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin and the like, Tris (1-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate and the like. From the viewpoint of the balance between curing reactivity and latency, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate are preferred, and tris (2-hydrazinocarbonylethyl) isocyanurate is particularly preferred.
The component (E) may be used alone or in combination of two or more. When the component (E) is used in the liquid crystal sealing agent of the present invention, the content is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the liquid crystal sealing agent.
The liquid crystal sealing agent of the present invention can be improved in adhesive strength and moisture resistance by adding a silane coupling agent as the component (F).
As the component (F), there may be mentioned: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) -3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane and the like. These silane coupling agents are sold by shin-Etsu chemical industries, Inc. in the form of KBM series, KBE series, etc., and thus can be easily obtained from the market. When the component (F) is used in the liquid crystal sealing agent of the present invention, it is preferably 0.05 to 3% by mass in the total amount of the liquid crystal sealing agent.
The liquid crystal sealing agent of the present invention may further contain additives such as a curing accelerator such as an organic acid and imidazole, a radical polymerization inhibitor, a pigment, a leveling agent, a defoaming agent, and a solvent, as required.
Examples of the curing accelerator include organic acids and imidazoles.
Examples of the organic acid include an organic carboxylic acid and an organic phosphoric acid, and an organic carboxylic acid is preferable. Specifically, there may be mentioned: aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, and furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, tris (2-carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, and bis (2-carboxyethyl) isocyanurate.
Further, as the imidazole compound, there can be mentioned: 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2, 4-diamino-6- (2 '-methylimidazole (1')) ethyl-s-triazine, 2, 4-diamino-6- (2 '-undecylimidazole (1')) ethyl-s-triazine, 2, 4-diamino-6- (2 '-ethyl-4-methylimidazole (1')) ethyl-s-triazine, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 1-methyl, 2, 4-diamino-6- (2 '-methylimidazole (1')) ethyl s-triazine-isocyanuric acid adduct, 2: 3 adduct, 2-phenylimidazole-isocyanuric acid adduct, 2-phenyl-3, 5-dimethylolimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3, 5-dicyanoethoxymethylimidazole and the like.
When the curing accelerator is used in the liquid crystal sealing agent of the present invention, the amount of the curing accelerator is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the liquid crystal sealing agent.
The radical polymerization inhibitor is not particularly limited as long as it is a compound that inhibits polymerization by reacting with a radical generated by a photoradical polymerization initiator, a thermal radical polymerization initiator, or the like, and quinones, piperidines, hindered phenols, nitroses, or the like can be used. Specifically, there may be mentioned: naphthoquinone, 2-hydroxynaphthoquinone, 2-menadione, 2-methoxynaphthoquinone, 2,6, 6-tetramethylpiperidine-1-oxyl, 2,6, 6-tetramethyl-4-hydroxypiperidine-1-oxyl, 2,6, 6-tetramethyl-4-methoxypiperidine-1-oxyl, 2,6, 6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, p-benzoquinone, butylated hydroxyanisole, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butylcresol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid stearyl ester, stearyl ester, 2,2 ' -methylenebis (4-ethyl-6-tert-butylphenol), 4' -thiobis (3-methyl-6-tert-butylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis [1, 1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, tetrakis [ methylene-3- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenylpropionate) methane, 1,3, 5-tris (3 ', 5 ' -di-tert-butyl-4 ' -hydroxybenzyl) -s-triazine-2, 4,6- (1H,3H,5H) trione, p-methoxyphenol, 4-methoxy-1-naphthol, phenothiazine, aluminum salt of N-nitrosophenylhydroxylamine, trade name ADK STAB LA-81, trade name ADK STABLA-82 (made by Edik corporation), and the like, but are not limited thereto. Among them, naphthoquinone, hydroquinone, nitroso, and piperazine radical polymerization inhibitors are preferable, naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2, 6-di-tert-butyl-P-cresol, POLYSTOP 7300P (available from bermuda corporation) is more preferable, and POLYSTOP 7300P (available from bermuda corporation) is most preferable.
The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and particularly preferably 0.01 to 0.2% by mass, based on the total amount of the liquid crystal sealing agent of the present invention.
As an example of a method for obtaining the liquid crystal sealing agent of the present invention, the following method is given. First, the component (C) is dissolved in the component (A) by heating as necessary. Subsequently, the liquid crystal sealing agent of the present invention can be produced by cooling to room temperature, adding the component (F) as needed, further adding the component (B), the component (D), the component (E), an antifoaming agent, a leveling agent, a solvent, and the like, uniformly mixing them by a known mixing device such as a three-roll mill, a sand mill, a ball mill, and the like, and filtering them with a metal mesh.
The liquid crystal display cell of the present invention is obtained by arranging a pair of substrates having predetermined electrodes formed on the substrates so as to face each other at a predetermined interval, sealing the periphery with the liquid crystal sealing agent of the present invention, and sealing liquid crystal in the gap. The type of the enclosed liquid crystal is not particularly limited. Herein, the substrateThe light-transmitting substrate is composed of a combination of substrates including glass, quartz, plastic, silicon, and the like, at least one of which is light-transmitting. As a method for producing the same, a spacer (gap control material) such as glass fiber is added to the liquid crystal sealing agent of the present invention, and then the liquid crystal sealing agent is applied to one of the pair of substrates by using a dispenser, a screen printing apparatus, or the like, and then precured at 80 to 120 ℃ as necessary. Then, liquid crystal is dropped inside the bank of the liquid crystal sealing agent, and another glass substrate is stacked in vacuum to form a gap. After the gap is formed, the cured product is cured at 90 to 130 ℃ for 1 to 2 hours, whereby the liquid crystal display cell of the present invention can be obtained. In the case of using the liquid crystal sealing material as a photo-thermal type, ultraviolet rays are irradiated to the liquid crystal sealing material portion by an ultraviolet ray irradiator to perform photo-curing. The ultraviolet irradiation dose is preferably 500 to 10000mJ/cm2More preferably 1000 to 6000mJ/cm2The irradiation amount of (3). Then, if necessary, the cured product is cured at 90 to 130 ℃ for 1 to 2 hours, whereby the liquid crystal display cell of the present invention can be obtained. The liquid crystal display cell of the present invention thus obtained is free from display defects caused by liquid crystal contamination and is excellent in adhesiveness and moisture resistance reliability. Examples of the spacer include glass fiber, silica beads, and polymer beads. The diameter thereof varies depending on the purpose, and is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of the liquid crystal sealing agent used is usually about 0.1 to about 4% by mass, preferably about 0.5 to about 2% by mass, and more preferably about 0.9 to about 1.5% by mass, based on 100% by mass of the liquid crystal sealing agent of the present invention.
The liquid crystal sealing agent has the effect of reducing the corrosion of wiring. As a result, the drive defect after the humidity resistance test can be eliminated. Further, the liquid crystal composition is excellent in low liquid crystal contamination, and the cured product thereof is excellent in various cured product properties such as adhesive strength and heat resistance. As described above, by using the liquid crystal sealing agent of the present invention, a liquid crystal display cell having excellent reliability can be realized. In addition, the liquid crystal display cell produced using the liquid crystal sealing agent of the present invention satisfies the characteristics required for a liquid crystal display cell, such as high voltage holding ratio and low ion density.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples. Unless otherwise specified, "part(s)" and "%" in the present specification are based on mass.
[ Synthesis example 1]
[ Synthesis of Peracrylates of Resorcinol diglycidyl Ether ]
[ Process 1]
5500g of resorcinol, 37000g of epichlorohydrin and 500g of tetramethylammonium chloride were charged into a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, and dissolved with stirring, and the temperature was raised to 70 ℃. Next, 4000g of flake-form sodium hydroxide was added stepwise over 100 minutes, followed by post-reaction at 70 ℃ for 1 hour. After the reaction, 15000g of water was added thereto to wash the resulting mixture with water, and then excess epichlorohydrin and the like were distilled off from the oil layer at 130 ℃ under reduced pressure. 22200g of methyl isobutyl ketone was added to the residue to dissolve it, and the temperature was raised to 70 ℃. 1000g of a 30% aqueous solution of sodium hydroxide was added under stirring to conduct a reaction for 1 hour, followed by washing with 5550g of water three times, and methyl isobutyl ketone was distilled off at 180 ℃ under reduced pressure to obtain 10550g of resorcinol diglycidyl ether. The epoxy equivalent of the obtained epoxy compound was 129 g/eq.
[ Process 2]
181.2g of resorcinol diglycidyl ether obtained in the above synthesis example 1 was dissolved in 266.8g of toluene, 0.8g of dibutylhydroxytoluene as a polymerization inhibitor was added thereto, and the temperature was raised to 60 ℃. Then, 117.5g of acrylic acid of 100% equivalent of epoxy group was added, followed by warming to 80 ℃, 0.6g of trimethylammonium chloride as a reaction catalyst was added thereto, and stirring was carried out at 98 ℃ for about 30 hours. The obtained reaction solution was washed with water, and toluene was distilled off, whereby 253g of the intended acrylic acid ester of resorcinol diglycidyl ether was obtained.
[ Synthesis example 2]
[ Synthesis of all-acrylic acid Compound of bisphenol A type epoxy Compound ]
282.5g of bisphenol A type epoxy compound (product name: YD-8125, manufactured by Nippon iron chemical Co., Ltd.) was dissolved in 266.8g of toluene, and 0.8g of dibutylhydroxytoluene as a polymerization inhibitor was added thereto, and the temperature was raised to 60 ℃. Then, 117.5g of acrylic acid of 100% equivalent of epoxy group was added, followed by heating to 80 ℃, 0.6g of trimethylammonium chloride as a reaction catalyst was added thereto, and stirred at 98 ℃ for about 30 hours, thereby obtaining a reaction liquid. This reaction solution was washed with water and toluene was distilled off to obtain 395g of an acrylic acid ester of a bisphenol A type epoxy compound as an object.
[ Synthesis example 3]
[ Synthesis of 1, 2-bis (trimethylsilyloxy) -1,1,2, 2-tetraphenylethane ]
100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo chemical Co., Ltd.) was dissolved in 350 parts of dimethylformamide. To this solution, 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (product of shin-Etsu chemical Co., Ltd.) as a silylating agent were added, and the mixture was heated to 70 ℃ and stirred for 2 hours. The resulting reaction liquid was cooled, and 200 parts of water was added while stirring to precipitate the product and deactivate the unreacted silylating agent. The precipitated product was isolated by filtration and then washed thoroughly with water. Subsequently, the obtained product was dissolved in acetone, and water was added thereto to recrystallize it, followed by purification. 105.6 parts of the aimed 1, 2-bis (trimethylsiloxy) -1,1,2, 2-tetraphenylethane were obtained (yield 88.3%).
The purity was 99.0% (area percentage) as a result of HPLC analysis.
[ preparations of examples 1 to 5 and comparative examples 1 to 4 ]
A photo radical polymerization initiator (component (C)) was added to a curable compound (component (a)) such as the compound synthesized in synthesis example 1 or the compound synthesized in synthesis example 2 at a ratio shown in table 1 below, and the mixture was dissolved by heating at 90 ℃. The mixture was cooled to room temperature, and a thermal radical polymerization initiator (component (B)), a silane coupling agent (component (F)), a thermal curing agent (component (E)), an organic filler (component (D-1)), an inorganic filler (component (D-2)), and the like were added thereto, stirred, dispersed by a three-roll mill, and filtered through a metal mesh (635 mesh) to prepare sealants for the liquid crystal dropping method (examples 1 to 5 and comparative examples 1 to 4).
[ Water absorption measurement ]
The liquid crystal sealants prepared in examples and comparative examples were sandwiched between polyethylene terephthalate (PET) films to prepare films having a thickness of 100 μm, the films were put into an oven at 130 ℃ for 1 hour to be cured, and after curing, the PET films were peeled off to obtain cured sealant films, which were then cut into strips of 20mm × 50mm, thereby preparing sample sheets. The obtained sample piece was stabilized at 25 ℃ and 50% RH for 24 hours according to JIS-K7209D method, and then the initial weight was measured, and water was absorbed at 60 ℃ and 90% RH for 24 hours, and then the weight was measured, and the weight was set as the weight after water absorption. After the measurement, the water absorption was calculated by the following formula.
Water absorption (%) ((post-water absorption weight (g) -initial weight (g))/initial weight (g)) × 100 (%)
[ measurement of moisture permeability ]
A cured sealant film was produced in the same manner as the water absorption rate, and cut into a square shape of 90mm × 90mm to prepare a sample piece. The sample sheet was subjected to moisture permeability measurement at 60 ℃ using a moisture permeability measuring apparatus Lyssy L80-5000 manufactured by Systech Illinois Inc. in accordance with JIS-K7129A.
[ evaluation of electrode Corrosion in high temperature and high humidity test ]
Using the liquid crystal sealing materials produced in examples and comparative examples, a liquid crystal cell for evaluation having a cell gap of 5 μm was produced, and the occurrence of electrode corrosion in a high temperature and high humidity test was confirmed. The test method is as follows.
To 2g of each liquid crystal sealing agent, 0.02g of glass fiber having a diameter of 5 μm as a spacer was added, mixed, stirred, defoamed, and filled in a 5ml syringe. On a glass substrate with an ITO transparent electrode, a liquid crystal sealant previously filled in a syringe was applied by a dispenser (SHOTMASTER300, manufactured by Wu-K.K.) in a rectangular seal pattern of 30mm × 40mm, and then droplets of liquid crystal (MLC-3007, manufactured by Merck) were dropped into the seal pattern frame. However, the device is not suitable for use in a kitchenThen, an in-plane spacer (NATCO spacer KSEB-525F: 5 μm in gap width after bonding manufactured by NATCO Co., Ltd.) was scattered and thermally fixed on another ITO glass substrate, and the substrate on which the liquid crystal was deposited was bonded in vacuum using a bonding apparatus, and then opened to the atmosphere to form a gap. In order to provide a wiring shading part which is difficult to irradiate ultraviolet rays in sealing, a metal halide lamp (manufactured by Youshiwang electric Co., Ltd.) was used to irradiate a low dose of 500mJ/cm2(at 100mW/cm2Irradiated with ultraviolet light for 5 seconds) to semi-cure the seal pattern, and then placed in an oven at 130 ℃ for 1 hour to thermally cure the seal pattern, thereby producing a liquid crystal cell for evaluation. The obtained liquid crystal cell for evaluation was put under high temperature and high humidity conditions of 60 ℃ and 90% RH for 240 hours with a sine wave voltage of 10V and 100Hz applied thereto by a function generator (FG-281, manufactured by TEXIO Technology), and then the seal portion for evaluation was observed with a microscope, thereby evaluating the electrode corrosion according to the following criteria.
O: no corrosion of the ITO electrode was observed in the seal periphery.
And (delta): corrosion of the ITO electrode was slightly observed in the seal periphery.
X: corrosion of the ITO electrode was observed in the seal periphery.
[ evaluation of contamination of liquid Crystal ]
About 100mg of the sealant was applied to the bottom of a 10ml vial, and then a liquid crystal (MLC-3007, manufactured by Merck) in an amount of 10 times that of each of the applied sealants was added from above. The resulting vial was heated, held at 130 ℃ for 1 hour, and then cooled for 30 minutes to reach room temperature. The respective liquid crystal supernatants were separated by decantation, and the resistance values were measured by a digital ultra high resistance meter (R8340: manufactured by Advantest corporation) and determined by the following criteria based on the resistivity values relative to the liquid crystal values without the sealant.
○：5.0×1012The above
△：5.0×1011Above and less than 5.0 x 1012
X: less than 5.01011
[ evaluation of curability of light-blocking portion ]
As shown in fig. 1, a liquid crystal sealing agent containing 1 wt% of 3 μm glass fiber was applied to the center of the glass substrate after etching the chrome plating layer, and the substrate was bonded to a counter substrate using a black matrix substrate and fixed by a clip (before ultraviolet irradiation). The chromium-etched glass substrate was irradiated with 3000mJ/cm light from the side of the substrate2Then, the bonded two substrates were peeled off, and the portion shielded from the light below the chrome was confirmed by a microscope to measure the curing width of the light-shielding portion
O: more than 30 μm
And (delta): 10 μm or more and less than 30 μm
X: less than 10 μm
[ Table 1]
Figure BDA0001034255340000221
A-1: peracrylic acid compound of Resorcinol diglycidyl ether (Synthesis example 1)
A-2: all-acrylic acid compound of bisphenol A type epoxy compound (Synthesis example 2)
A-3: caprolactone-modified (6 mol) dipentaerythritol hexaacrylate (manufactured by Nippon Chemicals, Ltd.: DPCA-60)
A-4: bisphenol A type epoxy resin (manufactured by Nippon Kabushiki Kaisha RE-310S)
A-5: bisphenol A type epoxy resin high molecular weight body (made by Nissian iron and gold chemical Co., Ltd.: YD-012)
A-6: ethylene oxide-modified bisphenol S type epoxy resin (synthesized according to the method described in Japanese patent No. 4211942)
B-1: 1, 2-bis (trimethylsilyloxy) -1,1,2, 2-tetraphenylethane (Synthesis example 3 finely pulverized with a jet mill to an average particle diameter of 1.9 μm)
B-2: polycondensate of 4,4' -azobis (4-cyanovaleric acid) and polyethylene glycol (molecular weight: 2000) (product of Wako pure chemical industries, Ltd.: VPE-0201)
C-1: reaction product of 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one
(synthesized by the method described in International publication No. 2006/027982.)
C-2: 1, 2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime) ] (manufactured by BASF: IRGACURE OXE-01)
C-3: 2, 4-Diethylthioxanthone (DETX-S, manufactured by Nippon Kagaku K.K.)
D-1-1: polymethacrylate organic fine particles (Iker Industrial Co., Ltd.: F-351S)
D-2-1: spherical silica (product of Xinyue chemical industry Co., Ltd.: X-24-9163A)
D-2-2: spherical silica (manufactured by Deshan of K.K.: サンシール SSP-07DM)
E-1: fine powder of tris (2-hydrazinocarbonylethyl) isocyanurate
(HCIC, manufactured by Finechem, Japan, and finely pulverized into 1.5 μm with a jet mill)
F-1: 3-glycidoxypropyltrimethoxysilane (JNC: Sila-Ace S-510)
F-2: n-2 (aminoethyl) 3-aminopropyltriethoxysilane (KBM-603, product of shin-Etsu chemical Co., Ltd.)
O-1: nitroso-piperidine derivative (POLYSTOP 7300P, manufactured by Bondo corporation)
O-2: isocyanuric acid tris (2-carboxyethyl) ester
(CIC acid, manufactured by Siguo Kasei Kogyo Co., Ltd., finely pulverized with a jet mill to an average particle size of 1.5 μm)
From the results shown in table 1, examples 1 to 5 in which the water absorption rate and the moisture permeability of the cured product obtained by heat alone were constant values or less showed no wiring corrosion and excellent low liquid crystal contamination. On the other hand, the liquid crystal sealing agent described in the comparative example had a problem in long-term reliability of the liquid crystal display cell due to corrosion of wiring. From this it can be said that: the invention of the present application is a liquid crystal sealing agent having excellent reliability after a moisture resistance test, and a liquid crystal display cell produced using the liquid crystal sealing agent has excellent reliability.
Industrial applicability
The liquid crystal sealing agent of the present invention has a very small influence on liquid crystal display characteristics, and therefore, can realize high definition, high-speed response, low-voltage driving, and long life of a liquid crystal display element. Further, since the adhesive strength and the moisture resistance reliability are excellent, a highly reliable liquid crystal display element can be manufactured.

Claims (8)

1. A liquid crystal sealing agent for a liquid crystal dropping method, which comprises (A) a curable compound, (B) a thermal radical polymerization initiator, (C) a photo radical polymerization initiator and (E) a thermal curing agent,
the curable compound of the component (A) is a mixture of an epoxy (meth) acrylate compound and an epoxy compound,
the thermal radical polymerization initiator of the component (B) is a benzopinacol thermal radical polymerization initiator,
the cured product obtained by heat curing at 130 ℃ for 1 hour without ultraviolet irradiation has a water absorption of 2.0% or less as measured according to JIS-K7209 and a moisture permeability of 130g/m as measured according to JIS-K7129224h or less.
2. The liquid crystal sealing agent for liquid crystal dropping method according to claim 1, further comprising (D) a filler, wherein the content of the filler in the total amount of the liquid crystal sealing agent is 20% by mass or more.
3. The liquid crystal sealant for liquid crystal dropping method according to claim 2, wherein the component (D) is a mixture of (D-1) an organic filler and (D-2) an inorganic filler.
4. The liquid crystal sealing agent for liquid crystal dropping method according to claim 3, wherein the content of the inorganic filler as the component (D-2) is 20% by mass or more in the total amount of the liquid crystal sealing agent.
5. The liquid crystal sealant for liquid crystal dropping method according to claim 1 or 2, wherein the component (E) heat curing agent is an organic hydrazide.
6. The liquid crystal sealant for liquid crystal dropping method as claimed in claim 1 or 2, further comprising (F) a silane coupling agent.
7. A method for manufacturing a liquid crystal display unit, characterized in that a liquid crystal is dropped on the inside of the bank of the liquid crystal sealing agent for the liquid crystal dropping method according to any one of claims 1 to 6 formed on one substrate in a liquid crystal display unit including two substrates, then the other substrate is attached, and then curing is performed by light and/or heat.
8. A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 6.
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